JP4530133B2 - Power storage device - Google Patents
Power storage device Download PDFInfo
- Publication number
- JP4530133B2 JP4530133B2 JP2004038721A JP2004038721A JP4530133B2 JP 4530133 B2 JP4530133 B2 JP 4530133B2 JP 2004038721 A JP2004038721 A JP 2004038721A JP 2004038721 A JP2004038721 A JP 2004038721A JP 4530133 B2 JP4530133 B2 JP 4530133B2
- Authority
- JP
- Japan
- Prior art keywords
- storage device
- chemical formula
- positive electrode
- polymer
- nitroxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、内部抵抗の小さな蓄電デバイスに関する。 The present invention relates to an electricity storage device having a low internal resistance.
正極活物質として、ニトロキシル高分子を利用する蓄電デバイスが提案されている。例えば、特許文献１の図１に記載されている従来の蓄電デバイスでは、ニトロキシル高分子を活物質とする正極を、アルミニウムもしくはステンレスといった正極用金属集電体の上に直接塗布、もしくは圧着させて蓄電デバイスを構築している。
しかしながら、この特許文献１に開示された蓄電デバイスには、蓄電デバイスの内部抵抗が高くなるという問題点がある。この原因は、アルミニウムもしくはステンレスといった金属集電体と、有機半導体であるニトロキシル高分子との間に、ショットキー型の内部抵抗が生じることに起因する。そのため、内部抵抗に起因するエネルギーの損失が大きくなってしまう。本発明の目的は、正極活物質としてニトロキシル高分子を用いた蓄電デバイスにおいて、内部抵抗の小さな蓄電デバイスを提供することにある。 However, the power storage device disclosed in Patent Document 1 has a problem that the internal resistance of the power storage device increases. This is because a Schottky-type internal resistance is generated between a metal current collector such as aluminum or stainless steel and a nitroxyl polymer that is an organic semiconductor. For this reason, energy loss due to internal resistance increases. An object of the present invention is to provide an electricity storage device having a small internal resistance in an electricity storage device using a nitroxyl polymer as a positive electrode active material.
［発明の特徴］
本発明の蓄電デバイスは、酸化状態において下記化学式（Ｉ）で示されるニトロキシルカチオン部分構造をとり、還元状態において下記化学式（ＩＩ）で示されニトロキシルラジカル部分構造をとるニトロキシル高分子を正極中に含有し、その２つの状態間で電子の授受を行う下記反応式（Ｂ）で示される反応を正極の電極反応として用いる蓄電デバイスであって、ニトロキシル高分子を含有する正極と、アルミニウムもしくはステンレスといった正極用金属集電体との間に、カーボンペーパーを有することを特徴としている。
[Features of the invention]
The electricity storage device of the present invention comprises a nitroxyl polymer having a nitroxyl cation partial structure represented by the following chemical formula (I) in an oxidized state and a nitroxyl radical partial structure represented by the following chemical formula (II) in a reduced state in a positive electrode. And an electron storage device that uses a reaction represented by the following reaction formula (B) as an electrode reaction of the positive electrode to transfer electrons between the two states, the positive electrode containing a nitroxyl polymer, and aluminum or stainless steel It is characterized by having carbon paper between the positive electrode metal current collector.
［作用］
ニトロキシル高分子を活物質とする正極と、アルミニウムもしくはステンレスといった正極用金属集電体との間に挟んだカーボンペーパーが、有機高分子化合物と金属集電体とのポテンシャル障壁を小さくする効果があるため、蓄電デバイスの内部抵抗が小さくなる。
[Action]
Carbon paper sandwiched between a positive electrode using a nitroxyl polymer as an active material and a positive electrode metal current collector such as aluminum or stainless steel has the effect of reducing the potential barrier between the organic polymer compound and the metal current collector. Therefore, the internal resistance of the electricity storage device is reduced.
本発明の効果は、ニトロキシル高分子を活物質とする正極と金属集電体との間にカーボンペーパーを挟むことで、内部抵抗の小さな蓄電デバイスを提供することができる。 The effect of the present invention is that a carbon paper is sandwiched between a positive electrode using a nitroxyl polymer as an active material and a metal current collector, thereby providing an electricity storage device with low internal resistance.
［構造］
次に、本発明の実施の形態について図面を参照して詳細に説明する。
[Construction]
Next, embodiments of the present invention will be described in detail with reference to the drawings.
図１を参照すると、本発明の第１の実施の形態として蓄電デバイスの概観図が示されている。 Referring to FIG. 1, an overview of an electricity storage device is shown as a first embodiment of the present invention.
本発明による蓄電デバイスは、例えば図１に示すような構成を有している。図１に示された蓄電デバイスは負極３と正極５とを電解質を含むセパレータ４を介して重ね合わせた構成を有しており、正極５と正極用金属集電体７との間にカーボンペーパー６を有していることを特徴としている。第１の実施の形態におけるカーボンペーパー６は、繊維状炭素を原料とした不織布構造をとっており、その厚みは０．１１ミリメートル、空隙率は８０％である。第１の実施の形態におけるカーボンペーパー６の室温における電気抵抗率は、厚み方向で８０ｍΩ・ｃｍ、面方向で６．３ｍΩ・ｃｍである。第１の実施の形態における負極用金属集電体１および正極用金属集電体７はステンレス板からなっており、ポリプロピレン製の絶縁パッキン２を挟んだコイン型蓄電デバイスの形状を有している。第１の実施の形態における負極３としてはリチウム金属を使用し、正極活物質としては、下記化学式（１）で示されるニトロキシル高分子、ポリ（２，２，６，６−テトラメチルピペリジノキシ メタクリレート）（ＰＴＭＡ）を用いている。正極活物質であるＰＴＭＡは、アセチレンブラックを主成分とする導電性付与剤およびポリテトラフルオロエチレンを主成分とするバインダーと複合化させて正極を形成している。それらの含有率は重量比で、ＰＴＭＡ／導電性付与剤／バインダー＝５／４／１の割合である。第１の実施の形態におけるセパレータ４としては、ポリプロピレン製の多孔質セパレータを用いている。第１の実施の形態における電解液としては、支持塩として１ＭのＬｉＰＦ6を含む、エチレンカーボネート（ＥＣ）およびジエチルカーボネート（ＤＥＣ）の混合溶媒（混合体積比ＥＣ／ＤＥＣ＝３／７）を用いている。 The power storage device according to the present invention has a configuration as shown in FIG. 1, for example. The power storage device shown in FIG. 1 has a configuration in which a negative electrode 3 and a positive electrode 5 are superposed via a separator 4 containing an electrolyte, and a carbon paper is interposed between the positive electrode 5 and the positive electrode metal current collector 7. 6 is a feature. The carbon paper 6 in 1st Embodiment has taken the nonwoven fabric structure which used the fibrous carbon as a raw material, The thickness is 0.11 millimeter and the porosity is 80%. The electrical resistivity at room temperature of the carbon paper 6 in the first embodiment is 80 mΩ · cm in the thickness direction and 6.3 mΩ · cm in the plane direction. The negative electrode metal current collector 1 and the positive electrode metal current collector 7 in the first embodiment are made of a stainless steel plate and have the shape of a coin-type electricity storage device with a polypropylene insulating packing 2 interposed therebetween. . Lithium metal is used as the negative electrode 3 in the first embodiment, and a nitroxyl polymer represented by the following chemical formula (1), poly (2,2,6,6-tetramethylpiperidino) is used as the positive electrode active material. Xymethacrylate) (PTMA) is used. PTMA, which is a positive electrode active material, is combined with a conductivity-imparting agent mainly composed of acetylene black and a binder mainly composed of polytetrafluoroethylene to form a positive electrode. Their content is in a weight ratio of PTMA / conductivity imparting agent / binder = 5/4/1. As the separator 4 in the first embodiment, a porous separator made of polypropylene is used. As the electrolytic solution in the first embodiment, a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (mixing volume ratio EC / DEC = 3/7) containing 1M LiPF 6 as a supporting salt is used. ing.
［製法］
次に図１を参照して、第１の実施の形態の製造方法を説明する。
[Production method]
Next, a manufacturing method according to the first embodiment will be described with reference to FIG.
還流管を付けた１００ｍｌナスフラスコ中に、２，２，６，６−テトラメチルピペリジン メタクリレート モノマー２０ｇ（０．０８９ｍｏｌ）を入れ、乾燥テトラヒドロフラン８０ｍｌに溶解させた。そこへ、アゾビスイソブチロニトリル（ＡＩＢＮ）０．２９ｇ（０．００１７８ｍｏｌ）（モノマー／ＡＩＢＮ＝５０／ｌ）を加え、アルゴン雰囲気下７５〜８０℃で攪拌した。６時間反応後、室温まで放冷した。へキサン中でポリマーを析出させて濾別し、減圧乾燥してポリ（２，２，６，６−テトラメチルピペリジン メタクリレート）１８ｇ（収率９０％）を得た。次に、得られたポリ（２，２，６，６−テトラメチルピペリジン メタクリレート）１０ｇを乾操ジクロロメタン１００ｍｌに溶解させた。ここへｍ−クロロ過安息香酸１５．２ｇ（０．０８８ｍｏｌ）のジクロロメタン溶液１００ｍｌを室温にて攪拌しながら１時間かけて滴下した。さらに６時間攪拌後、沈殿したｍ−クロロ安息香酸を濾別して除き、濾液を炭酸ナトリウム水溶液および水で洗浄後、ジクロロメタンを留去した。残った固形分を粉砕し、得られた粉末をジエチルカーボネート（ＤＥＣ）で洗浄し、減圧下乾燥させて、下記化学式（２）で示されるポリ（２，２，６，６−テトラメチルピペリジノキシ メタクリレート）（ＰＴＭＡ）７．２ｇを得た（収率６８．２％、茶褐色粉末）。得られた高分子の構造はＩＲで確認した。また、ＧＰＣにより測定した結果、重量平均分子量Ｍｗ＝８９０００、分散度Ｍｗ／Ｍｎ＝３．３０という値が得られた。ＥＳＲスペクトルにより求めたスピン濃度は２．２６×１０21ｓｐｉｎ／ｇであった。これはポリ（２，２，６，６−テトラメチルピペリジン メタクリレート）のＮ−Ｈ基が、Ｎ−Ｏラジカルへ９０％転化されると仮定した場合のスピン濃度と一致する。 In a 100 ml eggplant flask equipped with a reflux tube, 20 g (0.089 mol) of 2,2,6,6-tetramethylpiperidine methacrylate monomer was placed and dissolved in 80 ml of dry tetrahydrofuran. Thereto was added 0.29 g (0.00178 mol) of azobisisobutyronitrile (AIBN) (monomer / AIBN = 50 / l), and the mixture was stirred at 75 to 80 ° C. in an argon atmosphere. After reacting for 6 hours, it was allowed to cool to room temperature. A polymer was precipitated in hexane, separated by filtration, and dried under reduced pressure to obtain 18 g (yield 90%) of poly (2,2,6,6-tetramethylpiperidine methacrylate). Next, 10 g of the obtained poly (2,2,6,6-tetramethylpiperidine methacrylate) was dissolved in 100 ml of dry-treated dichloromethane. To this, 100 ml of a dichloromethane solution of 15.2 g (0.088 mol) of m-chloroperbenzoic acid was added dropwise over 1 hour with stirring at room temperature. After further stirring for 6 hours, the precipitated m-chlorobenzoic acid was removed by filtration, and the filtrate was washed with an aqueous sodium carbonate solution and water, and then dichloromethane was distilled off. The remaining solid content was pulverized, and the resulting powder was washed with diethyl carbonate (DEC), dried under reduced pressure, and poly (2,2,6,6-tetramethylpiperidin represented by the following chemical formula (2). Noxy methacrylate) (PTMA) 7.2g was obtained (yield 68.2%, brown powder). The structure of the obtained polymer was confirmed by IR. Moreover, as a result of measuring by GPC, the value of weight average molecular weight Mw = 89000 and dispersion degree Mw / Mn = 3.30 was obtained. The spin concentration determined by ESR spectrum was 2.26 × 10 21 spin / g. This is consistent with the spin concentration assuming that the N—H group of poly (2,2,6,6-tetramethylpiperidine methacrylate) is 90% converted to an N—O radical.
合成した化学式（２）のポリメタクリレート５００ｍｇと、アセチレンブラック４００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。１０分ほど乾式混合して得られた混合体を、圧力を掛けてローラー延伸して、厚さ２００μｍの薄型電極板を得た。薄型電極板を、真空中８０℃で一晩乾燥した後、直径１２ｍｍの円形に打ち抜ぬき、蓄電デバイス用電極として成型した。次に、得られた電極を電解液に浸して、電極中の空隙に電解液を染み込ませた。電解液としては、１ｍｏｌ／ｌのＬｉＰＦ6電解質塩を含むＥＣ／ＤＥＣ混合溶液を用いた。電解液を含浸させた電極を直径１２ｍｍの円形に打ち抜いた厚み０．１１ミリメートルの不織布構造カーボンペーパー上にのせて、正極用金属集電体上に置き、その上に同じく電解液を含浸させた多孔質フィルムセパレータを積層した。さらに負極となるリチウム金属板を積層し、絶縁パッキンで被覆された負極用金属集電体を重ね合わせた。こうして作られた積層体を、かしめ機によって圧力を加え、コイン型蓄電デバイスを得た。 500 mg of the synthesized polymethacrylate of chemical formula (2), 400 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were measured and mixed in an agate mortar. The mixture obtained by dry-mixing for about 10 minutes was roller-stretched under pressure to obtain a thin electrode plate having a thickness of 200 μm. The thin electrode plate was dried overnight at 80 ° C. in a vacuum, and then punched out into a circle having a diameter of 12 mm and molded as an electrode for an electricity storage device. Next, the obtained electrode was immersed in an electrolytic solution, and the electrolytic solution was infiltrated into voids in the electrode. As the electrolytic solution, an EC / DEC mixed solution containing 1 mol / l LiPF 6 electrolyte salt was used. The electrode impregnated with the electrolytic solution was placed on a non-woven structure carbon paper having a thickness of 0.11 mm punched out into a circle having a diameter of 12 mm, and placed on a metal current collector for positive electrode. A porous film separator was laminated. Furthermore, the lithium metal plate used as a negative electrode was laminated | stacked, and the metal collector for negative electrodes coat | covered with the insulating packing was piled up. Pressure was applied to the laminate thus produced with a caulking machine to obtain a coin-type electricity storage device.
［発明の他の実施の形態］
上記第１の実施の形態において、コイン型であった蓄電デバイスの形状を、従来公知の形状にすることができる。蓄電デバイス形状の例としては、電極の積層体あるいは巻回体を、金属ケース、樹脂ケース、あるいはラミネートフィルム等によって封止したものが挙げられる。また外観としては、円筒型、角型、コイン型、およびシート型等が挙げられる。
[Other Embodiments of the Invention]
In the first embodiment, the shape of the electricity storage device that was a coin type can be changed to a conventionally known shape. As an example of the shape of the electricity storage device, there may be mentioned a case where an electrode laminate or a wound body is sealed with a metal case, a resin case, a laminate film, or the like. Examples of the appearance include a cylindrical shape, a square shape, a coin shape, and a sheet shape.
上記第１の実施の形態において、不織布構造であったカーボンペーパーを、繊維状炭素を織ってできる布状構造のカーボンペーパーで構成することができる。本発明におけるカーボンペーパーとは、繊維状炭素を集積化させて平たく伸ばした材料の総称であり、大きく分けて不織布構造のものと布状構造のものとがある。カーボンペーパーの厚みは、一般に０．０３〜０．５０ミリメートル程度であるが、機械的強度を保つためには０．０５ミリメートル以上であることが好ましい。しかしながら、蓄電デバイスのエネルギー密度を高めるといった観点から言えば、カーボンペーパーの厚みは薄い方がよく、０．２５ミリメートル以下であることが好ましい。カーボンペーパーの空隙率は、一般に５０〜９０％程度であるが、正極との接触面積を大きくすると言う観点から７０％以上であることが好ましい。カーボンペーパーの室温における電気抵抗率は、蓄電デバイスの内部抵抗を小さくすると言う観点から、厚み方向で３００ｍΩ・ｃｍ以下、面方向で３０ｍΩ・ｃｍ以下であることが好ましい。 In the said 1st Embodiment, the carbon paper which was the nonwoven fabric structure can be comprised with the carbon paper of the cloth-like structure formed by weaving fibrous carbon. The carbon paper in the present invention is a general term for materials obtained by integrating and flattening fibrous carbon, and is roughly classified into a nonwoven fabric structure and a cloth structure. The thickness of the carbon paper is generally about 0.03 to 0.50 millimeters, but is preferably 0.05 millimeters or more in order to maintain mechanical strength. However, from the viewpoint of increasing the energy density of the electricity storage device, the thickness of the carbon paper is preferably thin, and is preferably 0.25 mm or less. The porosity of the carbon paper is generally about 50 to 90%, but is preferably 70% or more from the viewpoint of increasing the contact area with the positive electrode. The electrical resistivity at room temperature of the carbon paper is preferably 300 mΩ · cm or less in the thickness direction and 30 mΩ · cm or less in the plane direction from the viewpoint of reducing the internal resistance of the electricity storage device.
上記第１の実施の形態において、正極活物質であるＰＴＭＡを、従来公知のニトロキシル高分子で構成することができる。本発明におけるニトロキシル高分子とは、代表的構造として下記化学式（３）で示されるような、ニトロキシル構造を有する高分子化合物の総称であるが、ニトロキシル構造は、下記反応式（Ａ）で示されるように、電子の授受により化学式（Ｉ）〜（ＩＩＩ）の状態を取りうる。 In the first embodiment, PTMA, which is a positive electrode active material, can be composed of a conventionally known nitroxyl polymer. The nitroxyl polymer in the present invention is a generic name for polymer compounds having a nitroxyl structure as represented by the following chemical formula (3) as a typical structure, but the nitroxyl structure is represented by the following reaction formula (A). As described above, the states of chemical formulas (I) to (III) can be taken by the exchange of electrons.
本発明における蓄電デバイスは、化学式（Ｉ）と（ＩＩ）の間の反応を正極の電極反応として用い、それに伴う電子の蓄積と放出により蓄電効果を機能させるものである。ここで蓄電デバイスとは、少なくとも正極と負極を有し、電気化学的に蓄えられたエネルギーを電力の形で取り出すことのできるデバイスである。蓄電デバイスにおいて正極とは、酸化還元電位が高い電極のことであり、負極とは逆に酸化還元電位が低い方の電極のことである。 The electricity storage device in the present invention uses the reaction between the chemical formulas (I) and (II) as the electrode reaction of the positive electrode, and functions the electricity storage effect by accumulating and releasing electrons associated therewith. Here, the electricity storage device is a device having at least a positive electrode and a negative electrode and capable of taking out electrochemically stored energy in the form of electric power. In the electricity storage device, the positive electrode is an electrode having a higher redox potential, and the negative electrode is an electrode having a lower redox potential.
本発明において、酸化状態おけるニトロキシル構造としては下記化学式（５）で示される環状ニトロキシル構造が好ましい。還元状態においては、化学式（５）のニトロキシル部分が式（ＩＩ）のニトロキシルラジカル構造となっている。Ｒ1〜Ｒ4は、それぞれ独立にアルキル基を表し、特に直鎖状のアルキル基が好ましい。また、ラジカルの安定性の点で炭素数は１〜４のアルキル基が好ましく、特にメチル基が好ましい。基Ｘにおいて環員を構成する原子は、炭素、酸素、窒素、および硫黄からなる群より選ばれる。基Ｘとしては化学式（５）が５〜７員環を形成するような２価の基を表し、具体的には、−ＣＨ2ＣＨ2−、−ＣＨ2ＣＨ2ＣＨ2−、−ＣＨ2ＣＨ2ＣＨ2ＣＨ2−、−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨＣＨ2−、−ＣＨ＝ＣＨＣＨ2ＣＨ2−、−ＣＨ2ＣＨ＝ＣＨＣＨ2−が挙げられ、その中で、隣接しない−ＣＨ2−は、−Ｏ−、−ＮＨ−または−Ｓ−によって置き換えられていてもよく、−ＣＨ＝は−Ｎ＝によって置き換えられていてもよい。また、環を構成する原子に結合した水素原子は、アルキル基、ハロゲン原子、＝Ｏ等により置換されていてもよい。 In the present invention, the nitroxyl structure in the oxidized state is preferably a cyclic nitroxyl structure represented by the following chemical formula (5). In the reduced state, the nitroxyl moiety of chemical formula (5) has a nitroxyl radical structure of formula (II). R 1 to R 4 each independently represents an alkyl group, and a linear alkyl group is particularly preferable. Further, from the viewpoint of radical stability, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable. The atom constituting the ring member in the group X is selected from the group consisting of carbon, oxygen, nitrogen, and sulfur. The group X represents a divalent group in which the chemical formula (5) forms a 5- to 7-membered ring, specifically, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2. CH 2 CH 2 CH 2 —, —CH═CH—, —CH═CHCH 2 —, —CH═CHCH 2 CH 2 —, —CH 2 CH═CHCH 2 —, among which —CH 2 — may be replaced by —O—, —NH— or —S—, and —CH═ may be replaced by —N═. In addition, a hydrogen atom bonded to an atom constituting the ring may be substituted with an alkyl group, a halogen atom, ═O, or the like.
特に好ましい環状ニトロキシル構造は酸化状態において、化学式（６）で示される２，２，６，６−テトラメチルピペリジノキシルカチオン、化学式（７）で示される２，２，５，５−テトラメチルピロリジノキシルカチオン、および化学式（８）で示される２，２，５，５−テトラメチルピロリノキシルカチオンからなる群より選ばれるものである。 Particularly preferred cyclic nitroxyl structures are 2,2,6,6-tetramethylpiperidinoxyl cation represented by the chemical formula (6), 2,2,5,5-tetramethyl represented by the chemical formula (7) in the oxidized state. It is selected from the group consisting of pyrrolidinoxyl cation and 2,2,5,5-tetramethylpyrrolinoxyl cation represented by chemical formula (8).
ただし、本発明において、上記の化学式（５）で示される環状ニトロキシル構造は、側鎖もしくは主鎖の一部としてポリマーの一部を構成している。すなわち、環状構造を形成する元素に結合する少なくとも１つの水素を取った構造としてポリマーの側鎖もしくは主鎖の一部に存在している。合成等の容易さから側鎖に存在している方が好ましい。側鎖に存在するときは、下記化学式（９）に示すように、化学式（５）の基Ｘ中の環員を構成する−ＣＨ2−、−ＣＨ＝または−ＮＨ−から水素を取った残基Ｘ’によって主鎖ポリマーに結合している。 However, in the present invention, the cyclic nitroxyl structure represented by the above chemical formula (5) constitutes a part of the polymer as a part of the side chain or main chain. That is, it exists in a part of the side chain or main chain of the polymer as a structure in which at least one hydrogen bonded to the element forming the cyclic structure is removed. It is preferable to be present in the side chain from the viewpoint of ease of synthesis and the like. When present in the side chain, as shown in the following chemical formula (9), a residue obtained by removing hydrogen from —CH 2 —, —CH═ or —NH— constituting the ring member in the group X of the chemical formula (5). It is connected to the main chain polymer by a group X ′.
（式中、Ｒ1〜Ｒ4は前記化学式（５）と同義である。）
このとき用いられる主鎖ポリマーとしては特に制限はなく、どのようなものであっても、化学式（９）の環状ニトロキシル構造を有する残基が側鎖に存在していればよい。具体的には、次に挙げるポリマーに、化学式（９）の残基が付加したもの、またはポリマーの一部の原子または基が、化学式（９）の残基によって置換されたものを挙げることができる。いずれの場合も、化学式（９）の残基が直接ではなく、適当な２価の基を中間に介して結合していてもよい。例えば、ポリエチレン、ポリプロピレン、ポリブテン、ポリデセン、ポリドデセン、ポリヘプテン、ポリイソブテン、ポリオクタデセン等のポリアルキレン系ポリマー；ポリブタジエン、ポリクロロプレン、ポリイソプレン、ポリイソブテン等のジエン系ポリマー；ポリ（メタ）アクリル酸；ポリ（メタ）アクリロニトリル；ポリ（メタ）アクリルアミド、ポリメチル（メタ）アクリルアミド、ポリジメチル（メタ）アクリルアミド、ポリイソプロピル（メタ）アクリルアミド等のポリ（メタ）アクリルアミド類ポリマー；ポリメチル（メタ）アクリレート、ポリエチル（メタ）アクリレート、ポリブチル（メタ）アクリレート等のポリアルキル（メタ）アクリレート類；ポリフッ化ビニリデン、ポリテトラフルオロエチレン等のフッ素系ポリマー；ポリスチレン、ポリブロモスチレン、ポリクロロスチレン、ポリメチルスチレン等のポリスチレン系ポリマー；ポリビニルアセテート、ポリビニルアルコール、ポリ塩化ビニル、ポリビニルメチルエーテル、ポリビニルカルバゾール、ポリビニルピリジン、ポリビニルピロリドン等のビニル系ポリマー；ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリブテンオキサイド、ポリオキシメチレン、ポリアセトアルデヒド、ポリメチルビニルエーテル、ポリプロピルビニルエーテル、ポリブチルビニルエーテル、ポリベンジルビニルエーテル等のポリエーテル系ポリマー；ポリメチレンスルフィド、ポリエチレンスルフィド、ポリエチレンジスルフィド、ポリプロピレンスルフィド、ポリフェニレンスルフィド、ポリエチレンテトラフルフィド、ポリエチレントリメチレンスルフィド等のポリスルフィド系ポリマー；ポリエチレンテレフタレート、ポリエチレンアジペート、ポリエチレンイソフタレート、ポリエチレンナフタレート、ポリエチレンパラフェニレンジアセテート、ポリエチレンイソプロピリデンジベンゾエート等のポリエステル類；ポリトリメチレンエチレンウレタン等のポリウレタン類；ポリエーテルケトン、ポリアリルエーテルケトン等のポリケトン系ポリマー；ポリオキシイソフタロイル等のポリ無水物系ポリマー；ポリエチレンアミン、ポリヘキサメチレンアミン、ポリエチレントリメチレンアミン等のポリアミン系ポリマー；ナイロン、ポリグリシン、ポリアラニン等のポリアミド系ポリマー；ポリアセチルイミノエチレン、ポリベンゾイルイミノエチレン等のポリイミン系ポリマー；ポリエステルイミド、ポリエーテルイミド、ポリベンズイミド、ポリピロメルイミド等のポリイミド系ポリマー；ポリアリレン、ポリアリレンアルキレン、ポリアリレンアルケニレン、ポリフェノール、フェノール樹脂、セルロース、ポリベンゾイミダゾール、ポリベンゾチアゾール、ポリベンゾキサジン、ポリベンゾキサゾール、オリカルボラン、ポリジベンゾフラン、ポリオキソイソインドリン、ポリフランテトラカルボキシル酸ジイミド、ポリオキサジアゾール、ポリオキシンドール、ポリフタラジン、ポリフタライド、ポリシアヌレート、ポリイソシアヌレート、ポリピペラジン、ポリピペリジン、ポリピラジノキノキサン、ポリピラゾール、ポリピリダジン、ポリピリジン、ポリピロメリチミン、ポリキノン、ポリピロリジン、ポリキノキサリン、ポリトリアジン、ポリトリアゾール等のポリアロマティック系ポリマー；ポリジシロキサン、ポリジメチルシロキサン等のシロキサン系ポリマー；ポリシラン系ポリマー；ポリシラザン系ポリマー；ポリホスファゼン系ポリマー；ポリチアジル系ポリマー；ポリアセチレン、ポリピロール、ポリアニリン等の共役系ポリマーを挙げることができる。なお、（メタ）アクリルとはメタクリルまたはアクリルを意味する。
(In the formula, R 1 to R 4 have the same meanings as the chemical formula (5).)
There is no restriction | limiting in particular as a main chain polymer used at this time, What kind of thing should just have the residue which has the cyclic nitroxyl structure of Chemical formula (9) in a side chain. Specifically, the following polymers may be those in which a residue of chemical formula (9) is added, or those in which some atoms or groups of the polymer are substituted with residues of chemical formula (9). it can. In any case, the residue of the chemical formula (9) may be bonded via an appropriate divalent group in the middle instead of directly. For example, polyalkylene polymers such as polyethylene, polypropylene, polybutene, polydecene, polydodecene, polyheptene, polyisobutene and polyoctadecene; diene polymers such as polybutadiene, polychloroprene, polyisoprene and polyisobutene; poly (meth) acrylic acid; poly ( (Meth) acrylonitrile; poly (meth) acrylamide polymers such as poly (meth) acrylamide, polymethyl (meth) acrylamide, polydimethyl (meth) acrylamide, polyisopropyl (meth) acrylamide; polymethyl (meth) acrylate, polyethyl (meth) acrylate , Polyalkyl (meth) acrylates such as polybutyl (meth) acrylate; fluorine-based polymers such as polyvinylidene fluoride and polytetrafluoroethylene Polystyrene; polystyrene polymers such as polystyrene, polybromostyrene, polychlorostyrene, and polymethylstyrene; vinyl polymers such as polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl methyl ether, polyvinyl carbazole, polyvinyl pyridine, and polyvinyl pyrrolidone; polyethylene Polyether polymers such as oxide, polypropylene oxide, polybutene oxide, polyoxymethylene, polyacetaldehyde, polymethyl vinyl ether, polypropyl vinyl ether, polybutyl vinyl ether, polybenzyl vinyl ether; polymethylene sulfide, polyethylene sulfide, polyethylene disulfide, polypropylene sulfide, Polyphenylene sulfide, polyethylene Polysulfide polymers such as traflufide and polyethylene trimethylene sulfide; Polyesters such as polyethylene terephthalate, polyethylene adipate, polyethylene isophthalate, polyethylene naphthalate, polyethylene paraphenylene diacetate, polyethylene isopropylidene dibenzoate; Polyurethanes such as polytrimethylene ethylene urethane Polyketone polymers such as polyetherketone and polyallyletherketone; polyanhydride polymers such as polyoxyisophthaloyl; polyamine polymers such as polyethyleneamine, polyhexamethyleneamine and polyethylenetrimethyleneamine; nylon, poly Polyamide polymers such as glycine and polyalanine; polyacetyliminoethylene, polybenzoyl Polyimine polymers such as iminoethylene; Polyimide polymers such as polyesterimide, polyetherimide, polybenzimide, polypyromerimide; polyarylene, polyarylenealkylene, polyarylenealkenylene, polyphenol, phenolic resin, cellulose, polybenzo Imidazole, polybenzothiazole, polybenzoxazine, polybenzoxazole, olicarborane, polydibenzofuran, polyoxoisoindoline, polyfurantetracarboxylic acid diimide, polyoxadiazole, polyoxindole, polyphthalazine, polyphthalide, polycyanurate, Polyisocyanurate, polypiperazine, polypiperidine, polypyrazinoquinoxane, polypyrazole, polypyridazine, polypyridine, polypyrrole Polyaromatic polymers such as thymine, polyquinone, polypyrrolidine, polyquinoxaline, polytriazine, and polytriazole; siloxane polymers such as polydisiloxane and polydimethylsiloxane; polysilane polymers; polysilazane polymers; polyphosphazene polymers; polythiazyl polymers Polymers: Conjugated polymers such as polyacetylene, polypyrrole and polyaniline can be mentioned. In addition, (meth) acryl means methacryl or acrylic.
この中で、主鎖が電気化学的な耐性に優れている点で、ポリアルキレン系ポリマー、ポリ（メタ）アクリル酸、ポリ（メタ）アクリルアミド類ポリマー、ポリアルキル（メタ）アクリレート類、ポリスチレン系ポリマーが好ましい。主鎖とは、高分子化合物中で、最も炭素数の多い炭素鎖のことである。この中でも、酸化状態で下記化学式（１０）で示される単位を含むことができるように、ポリマーが選ばれることが好ましい。 Of these, polyalkylene polymers, poly (meth) acrylic acid, poly (meth) acrylamides polymers, polyalkyl (meth) acrylates, polystyrene polymers in that the main chain is excellent in electrochemical resistance. Is preferred. The main chain is a carbon chain having the largest number of carbon atoms in the polymer compound. Among these, it is preferable that the polymer is selected so that the unit represented by the following chemical formula (10) can be included in the oxidized state.
ここで、Ｒ1〜Ｒ4は前記化学式（５）と同義である。Ｒ5は、水素またはメチル基である。Ｙは特に限定はないが、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＲ6−、−Ｏ−、−Ｓ−、置換基を有していてもよい炭素数１〜１８のアルキレン基、置換基を有していてもよい炭素数１〜１８のアリーレン基、およびこれらの基の２つ以上を結合させた２価の基を挙げることができる。Ｒ6は、炭素数１〜１８のアルキル基を表す。化学式（１０）で表される単位で、特に好ましいものは、次の化学式（１１）〜（１４）で表されるものである。 Here, R < 1 > -R < 4 > is synonymous with the said Chemical formula (5). R 5 is hydrogen or a methyl group. Y is not particularly limited, but -CO-, -COO-, -CONR 6- , -O-, -S-, an optionally substituted alkylene group having 1 to 18 carbon atoms, and a substituent. The C1-C18 arylene group which may have and the bivalent group which couple | bonded two or more of these groups can be mentioned. R 6 represents an alkyl group having 1 to 18 carbon atoms. Of the units represented by the chemical formula (10), particularly preferred are those represented by the following chemical formulas (11) to (14).
化学式（１１）〜（１４）において、Ｙとしては、上記化学式（１０）と同義であるが、特に−ＣＯＯ−および−ＣＯＮＲ6−のいずれかが好ましい。 In the chemical formulas (11) to (14), Y has the same meaning as the chemical formula (10), and either —COO— or —CONR 6 — is particularly preferable.
本発明において、化学式（９）の残基が、側鎖のすべてに存在しなくても良い。例えばポリマーを構成する単位のすべてが化学式（１０）で示される単位であっても、または一部が化学式（１０）で示される単位であってもいずれでもよい。ポリマー中にどの程度含まれるかは、目的、ポリマーの構造、製造方法に異なるが、わずかでも存在していれば良く、通常１重量％以上、特に１０重量％以上が好ましい。ポリマー合成に特に制限が無く、またできるだけ大きな蓄電作用を得たい場合には、５０重量％以上、特に８０重量％以上が好ましい。 In the present invention, the residue of chemical formula (9) may not be present in all of the side chains. For example, all of the units constituting the polymer may be units represented by the chemical formula (10), or some of them may be units represented by the chemical formula (10). The amount contained in the polymer differs depending on the purpose, the structure of the polymer, and the production method, but it may be present even in a slight amount, and is usually 1% by weight or more, particularly preferably 10% by weight or more. There is no particular limitation on the polymer synthesis, and when it is desired to obtain as large a power storage effect as possible, it is preferably 50% by weight or more, particularly 80% by weight or more.
このようなポリマーを合成するには、例えば下記化学式（１５）で示されるモノマーを単独重合またはアルキルアクリレート等の共重合しうるモノマーとの共重合によりポリマーを得た後、−ＮＨ−部分を酸化することで、酸化状態において化学式（１０）で示される単位を有するポリマーを得ることができる。 In order to synthesize such a polymer, for example, a monomer represented by the following chemical formula (15) is homopolymerized or copolymerized with a copolymerizable monomer such as alkyl acrylate, and then the —NH— moiety is oxidized. By doing so, a polymer having a unit represented by the chemical formula (10) in an oxidized state can be obtained.
また、例えば、メタクリル酸等を重合してベースとなるポリマーを合成した後に、高分子反応により化学式（９）で示される残基（あるいはＮＯラジカルに酸化される前の−ＮＨ−を有する残基）を導入しても良い。 Further, for example, after synthesizing a base polymer by polymerizing methacrylic acid or the like, a residue represented by the chemical formula (9) by a polymer reaction (or a residue having —NH— before being oxidized to NO radicals) ) May be introduced.
本発明におけるニトロキシル高分子の分子量は特に制限はないが、電解質に溶けないだけの分子量を有していることが好ましく、これは電解質中の有機溶媒の種類との組み合わせにより異なる。一般には、重量平均分子量１，０００以上であり、好ましくは１０，０００以上、特に１００，０００以上である。本発明では、粉体として正極に混合することができるので、分子量はいくら大きくてもよい。一般的には重量平均分子量５，０００，０００以下である。また、化学式（９）で示される残基を含むポリマーは、架橋していてもよく、それにより電解質に対する耐久性を向上させることができる。 The molecular weight of the nitroxyl polymer in the present invention is not particularly limited, but preferably has a molecular weight that does not dissolve in the electrolyte, and this varies depending on the combination with the type of organic solvent in the electrolyte. Generally, the weight average molecular weight is 1,000 or more, preferably 10,000 or more, particularly 100,000 or more. In the present invention, the molecular weight can be as large as it can be mixed with the positive electrode as powder. Generally, the weight average molecular weight is 5,000,000 or less. Moreover, the polymer containing the residue represented by the chemical formula (9) may be cross-linked, thereby improving the durability against the electrolyte.
上記第１の実施の形態において、５０重量％であった正極中におけるニトロキシル高分子の含有率は、任意に調整することができる。正極中におけるニトロキシル高分子の主要な機能は、蓄電に寄与する活物質としての役割である。従って、従来の蓄電デバイス、例えば従来の電池の正極活物質の全量を本発明で規定するニトロキシル高分子に置き換えることができる。正極重量全体に対して、１０重量％以上であれば十分に効果が見られる。さらに、できるだけ大きな蓄電作用を得たい場合には、５０重量％以上、特に８０重量％以上であり、１００重量％とすることも好ましい。 In the first embodiment, the content of the nitroxyl polymer in the positive electrode, which was 50% by weight, can be arbitrarily adjusted. The main function of the nitroxyl polymer in the positive electrode is a role as an active material contributing to power storage. Therefore, the total amount of the positive electrode active material of a conventional electricity storage device, for example, a conventional battery can be replaced with the nitroxyl polymer defined in the present invention. A sufficient effect is seen if it is 10% by weight or more based on the total weight of the positive electrode. Furthermore, when it is desired to obtain a power storage effect as large as possible, it is 50% by weight or more, particularly 80% by weight or more, and preferably 100% by weight.
上記第１の実施の形態において、ＰＴＭＡのみであった正極活物質を、異種正極活物質と組み合わせて正極を構成することができる。異種正極活物質成分としては蓄電デバイス電極材料として従来高知のものが利用できる。このようなものとして、例えば、活性炭やグラファイト、カーボンブラック、アセチレンブラック等の炭素材料、ＬｉＭｎＯ2、ＬｉＣｏＯ2、ＬｉＮｉＯ2、あるいはＬｉxＶ2Ｏ5（０＜ｘ＜２）等の金属酸化物やポリアセチレン、ポリフェニレン、ポリアニリン、ポリピロール等の導電性高分子、ジスルフィド化合物等が挙げられる。 In the first embodiment, a positive electrode active material that is only PTMA can be combined with a different positive electrode active material to form a positive electrode. As the heterogeneous positive electrode active material component, conventionally known materials can be used as the power storage device electrode material. Examples of such materials include carbon materials such as activated carbon, graphite, carbon black, and acetylene black, and metal oxides such as LiMnO 2 , LiCoO 2 , LiNiO 2 , and Li x V 2 O 5 (0 <x <2). And conductive polymers such as polyacetylene, polyphenylene, polyaniline and polypyrrole, and disulfide compounds.
上記第１の実施の形態において、アセチレンブラックを主成分としていた導電性付与剤を、従来公知の導電性付与剤材料に置き換えて蓄電デバイスを構成することができる。従来公知の導電性付与剤としては、例えば、活性炭やグラファイト、カーボンブラック、ファーネスブラック、金属粉末等が挙げられる。 In the first embodiment, the electrical conductivity imparting agent based on acetylene black can be replaced with a conventionally known electrical conductivity imparting material to constitute an electricity storage device. Examples of conventionally known conductivity imparting agents include activated carbon, graphite, carbon black, furnace black, and metal powder.
上記第１の実施の形態において、テトラフルオロエチレンを用いていたバインダーを、従来公知のバインダーに置き換えて蓄電デバイスを構成することができる。従来公知のバインダーとしては、例えば、ポリフッ化ビニリデン、ビニリデンフロライド−ヘキサフルオロプロピレン共重合体、スチレン−ブタジエン共重合ゴム、ポリプロピレン、ポリエチレン、ポリイミド等の樹脂バインダー等が挙げられる。環状ニトロキシル構造を有するポリマーの主鎖の種類、環状ニトロキシル構造が付加されている側鎖の種類、または環状ニトロキシル構造を有していない側鎖の種類等によっては、バインダーの機能を兼ねることができる。その場合、従来のバインダーの使用が不要であったり、従来のバインダーの使用量を減らすことができる。あるいは、従来の活物質をそのまま使用し、バインダーとして環状ニトロキシル構造を有するポリマーを用いても良く、その場合にはバインダーに相当する量が活物質としても機能することになるので、それだけ高容量化を図ることができる。また、ポリマーの主鎖がポリアセチレン、ポリアニリン等の導電性ポリマーからなり、その側鎖に環状ニトロキシル構造が存在する場合には、環状ニトロキシル構造を有するポリマーが導電補助剤を兼ねることができる。この場合、従来の導電補助剤の使用が不要であったり、従来の導電補助剤の使用量を減らすことができる。あるいは、従来の活物質をそのまま使用し、導電補助剤として環状ニトロキシル構造を有するポリマーを用いても良く、その場合には導電補助剤に相当する量が活物質としても機能することになるので、それだけ高容量化を図ることができる。また、ニトロキシルカチオン構造は、例えば電解質中に含まれる水、アルコール等の不純物を不活性化する働きもあると考えられ、蓄電デバイスの性能劣化を抑制する働きもしている。いずれの場合も、環状ニトロキシル構造を有するポリマーは、有機溶媒等を含む電解質に対する溶解性が低く、耐久性が高いために特に効果が大きい。 In the first embodiment, the power storage device can be configured by replacing the binder that uses tetrafluoroethylene with a conventionally known binder. Examples of conventionally known binders include resin binders such as polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, styrene-butadiene copolymer rubber, polypropylene, polyethylene, and polyimide. Depending on the type of main chain of the polymer having a cyclic nitroxyl structure, the type of side chain to which the cyclic nitroxyl structure is added, or the type of side chain having no cyclic nitroxyl structure, it can also function as a binder. . In that case, the use of a conventional binder is unnecessary, and the amount of the conventional binder used can be reduced. Alternatively, a conventional active material may be used as it is, and a polymer having a cyclic nitroxyl structure may be used as a binder. In this case, the amount corresponding to the binder functions as the active material, so that the capacity is increased accordingly. Can be achieved. Further, when the polymer main chain is made of a conductive polymer such as polyacetylene or polyaniline and a cyclic nitroxyl structure is present in the side chain, the polymer having the cyclic nitroxyl structure can also serve as a conductive auxiliary. In this case, it is not necessary to use a conventional conductive auxiliary agent, and the amount of conventional conductive auxiliary agent used can be reduced. Alternatively, a conventional active material may be used as it is, and a polymer having a cyclic nitroxyl structure may be used as a conductive auxiliary. In this case, the amount corresponding to the conductive auxiliary functions as an active material, The capacity can be increased accordingly. Further, the nitroxyl cation structure is considered to have a function of inactivating impurities such as water and alcohol contained in the electrolyte, for example, and also has a function of suppressing performance deterioration of the electricity storage device. In any case, the polymer having a cyclic nitroxyl structure is particularly effective because it has low solubility in an electrolyte containing an organic solvent or the like and high durability.
上記第１の実施の形態において、リチウム金属を用いていた負極を、従来公知の負極に置き換えて蓄電デバイスを構成することができる。従来公知の負極としては、例えば、活性炭やグラファイト、カーボンブラック、アセチレンブラック等の炭素材料、リチウム合金、リチウムイオン吸蔵炭素、その他各種の金属単体や合金、ポリアセチレン、ポリフェニレン、ポリアニリン、ポリピロール等の導電性高分子、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ビニリデンフロライド−ヘキサフルオロプロピレン共重合体、スチレン−ブタジエン共重合ゴム、ポリプロピレン、ポリエチレン、ポリイミド等の樹脂バインダー、その他ジスルフィド化合物や触媒効果を示す化合物、イオン導電性高分子等が挙げられる。 In the first embodiment, the power storage device can be configured by replacing the negative electrode using lithium metal with a conventionally known negative electrode. Conventionally known negative electrodes include, for example, carbon materials such as activated carbon, graphite, carbon black, and acetylene black, lithium alloys, lithium ion storage carbon, and other various metal elements and alloys, polyacetylene, polyphenylene, polyaniline, polypyrrole, and other conductive materials. Polymer, polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, styrene-butadiene copolymer rubber, polypropylene, polyethylene, polyimide, and other resin binders, other disulfide compounds and compounds showing a catalytic effect, Examples thereof include ionic conductive polymers.
上記第１の実施の形態において、ステンレスを用いていた負極用金属集電体の材質を、従来公知の材質に置き換えて蓄電デバイスを構成することができる。従来公知の負極用金属集電体材質としては、例えば、ニッケルやアルミニウム、銅、金、銀、チタン、アルミニウム合金等の材質が挙げられる。また、形状としては、箔や平板、メッシュ状のものを用いることができる。 In the first embodiment, the material of the metal current collector for negative electrode, which uses stainless steel, can be replaced with a conventionally known material to constitute an electricity storage device. Examples of conventionally known metal current collector materials for negative electrodes include materials such as nickel, aluminum, copper, gold, silver, titanium, and aluminum alloys. Moreover, as a shape, a foil, a flat plate, or a mesh shape can be used.
上記第１の実施の形態において、ステンレスを用いていた正極用金属集電体の材質を、従来公知の材質に置き換えて蓄電デバイスを構成することができる。従来公知の正極用金属集電体材質としては、例えば、ニッケルやアルミニウム、銅、金、銀、チタン、アルミニウム合金等の材質が挙げられる。また、形状としては、箔や平板、メッシュ状のものを用いることができる。 In the first embodiment, the material of the positive electrode metal current collector using stainless steel can be replaced with a conventionally known material to constitute the electricity storage device. Examples of conventionally known positive electrode metal current collector materials include materials such as nickel, aluminum, copper, gold, silver, titanium, and aluminum alloys. Moreover, as a shape, a foil, a flat plate, or a mesh shape can be used.
上記第１の実施の形態において、１ｍｏｌ／ｌのＬｉＰＦ6電解質塩を含むＥＣ／ＤＥＣ混合溶液を使用していた電解質を、従来公知の電解質に置き換えて蓄電デバイスを構成することができる。電解質は、負極３と正極５との間の荷電担体輸送を行うものであり、一般には室温で１０-5〜１０-1Ｓ／ｃｍの電解質イオン伝導性を有している。従来公知の電解質としては、例えば電解質塩を溶剤に溶解した電解液を利用することができる。このような溶剤としては、例えばエチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、γ−ブチロラクトン、テトラヒドロフラン、ジオキソラン、スルホラン、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン等の有機溶媒、もしくは硫酸水溶液や水などが挙げられる。本発明ではこれらの溶剤を単独もしくは２種類以上混合して用いることもできる。また、電解質塩としては、例えばＬｉＰＦ6、ＬｉＣｌＯ4、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3、ＬｉＣ（Ｃ2Ｆ5ＳＯ2）3等が挙げられる。また、本発明に用いられる電解質としては固体電解質を用いても良い。これら固体電解質のうち、有機固体電解質材料としては、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体等のフッ化ビニリデン系重合体や、アクリロニトリル−メチルメタクリレート共重合体、アクリロニトリル−メチルアクリレート共重合体等のアクリルニトリル系重合体、さらにポリエチレンオキサイドなどが挙げられる。これらの高分子材料は、電解液を含ませてゲル状にして用いても、また電解質塩を含有させた高分子物質のみをそのまま用いても良い。一方、無機固体電解質としては、ＣａＦ2、ＡｇＩ、ＬｉＦ、βアルミナ、ガラス素材等が挙げられる。 In the first embodiment, an electrolyte using an EC / DEC mixed solution containing 1 mol / l LiPF 6 electrolyte salt can be replaced with a conventionally known electrolyte to constitute an electricity storage device. The electrolyte performs charge carrier transport between the negative electrode 3 and the positive electrode 5, and generally has an electrolyte ion conductivity of 10 −5 to 10 −1 S / cm at room temperature. As a conventionally well-known electrolyte, the electrolyte solution which melt | dissolved electrolyte salt in the solvent can be utilized, for example. Examples of such solvents include organic solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. A solvent, a sulfuric acid aqueous solution, water, etc. are mentioned. In the present invention, these solvents may be used alone or in combination of two or more. Examples of the electrolyte salt include LiPF 6 , LiClO 4 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3. , LiC (C 2 F 5 SO 2 ) 3 and the like. Moreover, you may use a solid electrolyte as an electrolyte used for this invention. Among these solid electrolytes, organic solid electrolyte materials include polyvinylidene fluoride, vinylidene fluoride-based polymers such as vinylidene fluoride-hexafluoropropylene copolymer, acrylonitrile-methyl methacrylate copolymer, acrylonitrile-methyl acrylate copolymer. Examples thereof include acrylonitrile polymers such as polymers, and polyethylene oxide. These polymer materials may be used in the form of a gel containing an electrolytic solution, or only a polymer material containing an electrolyte salt may be used as it is. On the other hand, examples of the inorganic solid electrolyte include CaF 2 , AgI, LiF, β-alumina, and a glass material.
上記第１の実施の形態において、ポリプロピレン製の多孔質フィルム用いていたセパレータの材質を、従来公知の材質に置き換えて蓄電デバイスを構成することができる。従来公知のセパレータの材質としては、例えば、ポリエチレン等の材質が挙げられる。 In the first embodiment, the electricity storage device can be configured by replacing the material of the separator used in the porous film made of polypropylene with a conventionally known material. As a material of a conventionally well-known separator, materials, such as polyethylene, are mentioned, for example.
次に具体的な実施例を用いて、実施の形態の製造方法を説明する。 Next, the manufacturing method of the embodiment will be described using specific examples.
＜環状ニトロキシル構造含有ポリマーの合成例＞
還流管を付けた１００ｍｌナスフラスコ中に、２，２，６，６−テトラメチルピペリジン メタクリレート モノマー２０ｇ（０．０８９ｍｏｌ）を入れ、乾燥テトラヒドロフラン８０ｍｌに溶解させた。そこへ、アゾビスイソブチロニトリル（ＡＩＢＮ）０．２９ｇ（０．００１７８ｍｏｌ）（モノマー／ＡＩＢＮ＝５０／ｌ）を加え、アルゴン雰囲気下７５〜８０℃で攪拌した。６時間反応後、室温まで放冷した。へキサン中でポリマーを析出させて濾別し、減圧乾燥してポリ（２，２，６，６−テトラメチルピペリジン メタクリレート）１８ｇ（収率９０％）を得た。次に、得られたポリ（２，２，６，６−テトラメチルピペリジン メタクリレート）１０ｇを乾操ジクロロメタン１００ｍｌに溶解させた。ここへｍ−クロロ過安息香酸１５．２ｇ（０．０８８ｍｏｌ）のジクロロメタン溶液１００ｍｌを室温にて攪拌しながら１時間かけて滴下した。さらに６時間攪拌後、沈殿したｍ−クロロ安息香酸を濾別して除き、濾液を炭酸ナトリウム水溶液および水で洗浄後、ジクロロメタンを留去した。残った固形分を粉砕し、得られた粉末をジエチルカーボネート（ＤＥＣ）で洗浄し、減圧下乾燥させて、下記化学式（１６）で示されるポリ（２，２，６，６−テトラメチルピペリジノキシ メタクリレート）（ＰＴＭＡ）７．２ｇを得た（収率６８．２％、茶褐色粉末）。得られた高分子の構造はＩＲで確認した。また、ＧＰＣにより測定した結果、重量平均分子量Ｍｗ＝８９０００、分散度Ｍｗ／Ｍｎ＝３．３０という値が得られた。ＥＳＲスペクトルにより求めたスピン濃度は２．２６×１０21ｓｐｉｎ／ｇであった。これはポリ（２，２，６，６−テトラメチルピペリジン メタクリレート）のＮ−Ｈ基が、Ｎ−Ｏラジカルへ９０％転化されると仮定した場合のスピン濃度と一致する。
<Synthesis example of cyclic nitroxyl structure-containing polymer>
In a 100 ml eggplant flask equipped with a reflux tube, 20 g (0.089 mol) of 2,2,6,6-tetramethylpiperidine methacrylate monomer was placed and dissolved in 80 ml of dry tetrahydrofuran. Thereto was added 0.29 g (0.00178 mol) of azobisisobutyronitrile (AIBN) (monomer / AIBN = 50 / l), and the mixture was stirred at 75 to 80 ° C. in an argon atmosphere. After reacting for 6 hours, it was allowed to cool to room temperature. A polymer was precipitated in hexane, separated by filtration, and dried under reduced pressure to obtain 18 g (yield 90%) of poly (2,2,6,6-tetramethylpiperidine methacrylate). Next, 10 g of the obtained poly (2,2,6,6-tetramethylpiperidine methacrylate) was dissolved in 100 ml of dry-treated dichloromethane. To this, 100 ml of a dichloromethane solution of 15.2 g (0.088 mol) of m-chloroperbenzoic acid was added dropwise over 1 hour with stirring at room temperature. After further stirring for 6 hours, the precipitated m-chlorobenzoic acid was removed by filtration, and the filtrate was washed with an aqueous sodium carbonate solution and water, and then dichloromethane was distilled off. The remaining solid content was pulverized, and the resulting powder was washed with diethyl carbonate (DEC), dried under reduced pressure, and poly (2,2,6,6-tetramethylpiperidin represented by the following chemical formula (16). Noxy methacrylate) (PTMA) 7.2g was obtained (yield 68.2%, brown powder). The structure of the obtained polymer was confirmed by IR. Moreover, as a result of measuring by GPC, the value of weight average molecular weight Mw = 89000 and dispersion degree Mw / Mn = 3.30 was obtained. The spin concentration determined by ESR spectrum was 2.26 × 10 21 spin / g. This is consistent with the spin concentration assuming that the N—H group of poly (2,2,6,6-tetramethylpiperidine methacrylate) is 90% converted to an N—O radical.
同様の方法で、下記化学式（１７）で示されるポリ（２，２，６，６−テトラメチルピペリジノキシ アクリレート）［重量平均分子量Ｍｗ＝７４０００、分散度Ｍｗ／Ｍｎ＝２．４５、スピン濃度：２．２３×１０21ｓｐｉｎ／ｇ（Ｎ−Ｈ基がＮ−Ｏラジカルへ８４％転化されると仮定した場合のスピン濃度と一致）］、化学式（１８）で示されるポリ（２，２，５，５−テトラメチルピロリジノキシ メタクリレート）［重量平均分子量Ｍｗ＝５２０００、分散度Ｍｗ／Ｍｎ＝３．５７、スピン濃度：１．９６×１０21ｓｐｉｎ／ｇ（Ｎ−Ｈ基がＮ−Ｏラジカルへ７４％転化されると仮定した場合のスピン濃度と一致）］、化学式（１９）で示されるポリ（２，２，５，５−テトラメチルピロリノキシ メタクリレート）［重量平均分子量Ｍｗ＝３３０００、分散度Ｍｗ／Ｍｎ＝４．０１、スピン濃度：２．０９×１０21ｓｐｉｎ／ｇ（Ｎ−Ｈ基がＮ−Ｏラジカルへ７８％転化されると仮定した場合のスピン濃度と一致）］を合成した。 In the same manner, poly (2,2,6,6-tetramethylpiperidinoxy acrylate) represented by the following chemical formula (17) [weight average molecular weight Mw = 74000, dispersity Mw / Mn = 2.45, spin Concentration: 2.23 × 10 21 spin / g (corresponding to the spin concentration when it is assumed that N—H group is converted to N—O radical by 84%)], poly (2, 2,5,5-tetramethylpyrrolidinoxy methacrylate) [weight average molecular weight Mw = 52000, dispersity Mw / Mn = 3.57, spin concentration: 1.96 × 10 21 spin / g (N—H group is N The same as the spin concentration assuming 74% conversion to —O radicals)], poly (2,2,5,5-tetramethylpyrrolinoxy methacrylate) represented by the chemical formula (19) [weight average molecular weight M = 33000, degree of dispersion Mw / Mn = 4.01, the spin concentration: 2.09 × 10 21 spin / g (N-H group is consistent with the spin concentration assuming that the conversion of 78% to N-O radical )] Was synthesized.
＜実施例１＞
合成した化学式（１６）のポリメタクリレート５００ｍｇと、アセチレンブラック４００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。１０分ほど乾式混合して得られた混合体を、圧力を掛けてローラー延伸して、厚さ２００μｍの薄型電極板を得た。薄型電極板を、真空中８０℃で一晩乾燥した後、直径１２ｍｍの円形に打ち抜ぬき、蓄電デバイス用電極として成型した。次に、得られた電極を電解液に浸して、電極中の空隙に電解液を染み込ませた。電解液としては、１ｍｏｌ／ｌのＬｉＰＦ6電解質塩を含むＥＣ／ＤＥＣ混合溶液（混合体積比ＥＣ／ＤＥＣ＝３／７）を用いた。電解液を含浸させた電極を直径１２ｍｍの円形に打ち抜いた厚み０．１１ミリメートルの不織布構造カーボンペーパー（空隙率：８０％、室温における電気抵抗率：８０ｍΩ・ｃｍ（厚み方向）、６．３ｍΩ・ｃｍ（面方向））上にのせて、正極用金属集電体（ステンレス板）上に置き、その上に同じく電解液を含浸させた多孔質フィルムセパレータ（ポリプロピレン製）を積層した。さらに負極となるリチウム金属板を積層し、絶縁パッキン（ポリプロピレン製）で被覆された負極用金属集電体（ステンレス板）を重ね合わせた。こうして作られた積層体を、かしめ機によって圧力を加え、コイン型蓄電デバイスを得た。
<Example 1>
500 mg of the synthesized polymethacrylate of chemical formula (16), 400 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. The mixture obtained by dry-mixing for about 10 minutes was roller-stretched under pressure to obtain a thin electrode plate having a thickness of 200 μm. The thin electrode plate was dried overnight at 80 ° C. in a vacuum, and then punched out into a circle having a diameter of 12 mm and molded as an electrode for an electricity storage device. Next, the obtained electrode was immersed in an electrolytic solution, and the electrolytic solution was infiltrated into voids in the electrode. As the electrolytic solution, an EC / DEC mixed solution (mixed volume ratio EC / DEC = 3/7) containing 1 mol / l LiPF 6 electrolyte salt was used. Electrode impregnated electrode is punched into a circular shape with a diameter of 12 mm and a non-woven structure carbon paper with a thickness of 0.11 mm (porosity: 80%, electrical resistivity at room temperature: 80 mΩ · cm (thickness direction), 6.3 mΩ · cm (surface direction)) and placed on a positive electrode metal current collector (stainless steel plate), and a porous film separator (made of polypropylene) impregnated with an electrolyte solution was laminated thereon. Furthermore, the lithium metal plate used as a negative electrode was laminated | stacked, and the metal collector for negative electrodes (stainless steel plate) coat | covered with the insulating packing (product made from a polypropylene) was piled up. Pressure was applied to the laminate thus produced with a caulking machine to obtain a coin-type electricity storage device.
＜実施例２＞
合成した化学式（１７）のポリアクリレート５００ｍｇと、アセチレンブラック４００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。それ以降は、実施例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Example 2>
500 mg of the synthesized polyacrylate of the chemical formula (17), 400 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. Thereafter, the same method as in Example 1 was performed to obtain a coin-type electricity storage device.
＜実施例３＞
合成した化学式（１８）のポリメタクリレート５００ｍｇと、アセチレンブラック４００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。それ以降は、実施例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Example 3>
500 mg of the synthesized polymethacrylate of chemical formula (18), 400 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. Thereafter, the same method as in Example 1 was performed to obtain a coin-type electricity storage device.
＜実施例４＞
合成した化学式（１９）のポリメタクリレート５００ｍｇと、アセチレンブラック４００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。それ以降は、実施例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Example 4>
500 mg of the synthesized polymethacrylate of chemical formula (19), 400 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. Thereafter, the same method as in Example 1 was performed to obtain a coin-type electricity storage device.
＜実施例５＞
負極としてグラファイト電極板を使用する以外は、実施例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Example 5>
Except using a graphite electrode plate as a negative electrode, it implemented by the method similar to Example 1, and obtained the coin-type electrical storage device.
＜実施例６＞
合成した化学式（１６）のポリメタクリレート１００ｍｇと、アセチレンブラック８００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。それ以降は、実施例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Example 6>
100 mg of the synthesized polymethacrylate of the chemical formula (16), 800 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. Thereafter, the same method as in Example 1 was performed to obtain a coin-type electricity storage device.
＜実施例７＞
合成した化学式（１６）のポリメタクリレート８００ｍｇと、アセチレンブラック１００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。それ以降は、実施例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Example 7>
800 mg of the synthesized polymethacrylate of chemical formula (16), 100 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. Thereafter, the same method as in Example 1 was performed to obtain a coin-type electricity storage device.
＜実施例８＞
厚み０．０５ミリメートルの不織布構造カーボンペーパー（空隙率：８２％、室温における電気抵抗率：８０ｍΩ・ｃｍ（厚み方向）、６．０ｍΩ・ｃｍ（面方向））を使用する以外は、実施例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Example 8>
Example 1 except that 0.05 mm-thick non-woven structure carbon paper (porosity: 82%, room temperature electrical resistivity: 80 mΩ · cm (thickness direction), 6.0 mΩ · cm (plane direction)) is used. In the same manner as above, a coin-type electricity storage device was obtained.
＜実施例９＞
厚み０．２５ミリメートルの不織布構造カーボンペーパー（空隙率：７８％、室温における電気抵抗率：８０ｍΩ・ｃｍ（厚み方向）、５．６ｍΩ・ｃｍ（面方向））を使用する以外は、実施例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Example 9>
Example 1 with the exception of using a non-woven carbon paper with a thickness of 0.25 mm (porosity: 78%, electrical resistivity at room temperature: 80 mΩ · cm (thickness direction), 5.6 mΩ · cm (plane direction)). In the same manner as above, a coin-type electricity storage device was obtained.
＜実施例１０＞
厚み０．２５ミリメートルの布状構造カーボンペーパー（空隙率：６８％、室温における電気抵抗率：２４０ｍΩ・ｃｍ（厚み方向）、１４ｍΩ・ｃｍ（面方向））を使用する以外は、実施例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Example 10>
Example 1 with the exception of using a 0.25 mm thick cloth-like carbon paper (porosity: 68%, electrical resistivity at room temperature: 240 mΩ · cm (thickness direction), 14 mΩ · cm (plane direction)) It implemented by the same method and obtained the coin-type electrical storage device.
＜比較例１＞
カーボンペーパーを用いずに、電解液を含浸させた電極を正極用金属集電体上に直接置く以外は、実施例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Comparative Example 1>
A coin-type electricity storage device was obtained in the same manner as in Example 1 except that the electrode impregnated with the electrolytic solution was placed directly on the positive electrode metal current collector without using carbon paper.
＜比較例２＞
合成した化学式（１７）のポリアクリレート５００ｍｇと、アセチレンブラック４００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。それ以降は、比較例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Comparative example 2>
500 mg of the synthesized polyacrylate of the chemical formula (17), 400 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. Thereafter, the same method as in Comparative Example 1 was performed to obtain a coin-type electricity storage device.
＜比較例３＞
合成した化学式（１８）のポリメタクリレート５００ｍｇと、アセチレンブラック４００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。それ以降は、比較例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Comparative Example 3>
500 mg of the synthesized polymethacrylate of chemical formula (18), 400 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. Thereafter, the same method as in Comparative Example 1 was performed to obtain a coin-type electricity storage device.
＜比較例４＞
合成した化学式（１９）のポリメタクリレート５００ｍｇと、アセチレンブラック４００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。それ以降は、比較例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Comparative example 4>
500 mg of the synthesized polymethacrylate of chemical formula (19), 400 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. Thereafter, the same method as in Comparative Example 1 was performed to obtain a coin-type electricity storage device.
＜比較例５＞
負極としてグラファイト電極板を使用する以外は、比較例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Comparative Example 5>
A coin-type electricity storage device was obtained in the same manner as in Comparative Example 1 except that a graphite electrode plate was used as the negative electrode.
＜比較例６＞
合成した化学式（１６）のポリメタクリレート１００ｍｇと、アセチレンブラック８００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。それ以降は、比較例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Comparative Example 6>
100 mg of the synthesized polymethacrylate of the chemical formula (16), 800 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. Thereafter, the same method as in Comparative Example 1 was performed to obtain a coin-type electricity storage device.
＜比較例７＞
合成した化学式（１６）のポリメタクリレート８００ｍｇと、アセチレンブラック１００ｍｇ、ポリテトラフルオロエチレン樹脂バインダ１００ｍｇを測り採り、メノウ乳鉢で混合した。それ以降は、比較例１と同様の方法で実施し、コイン型蓄電デバイスを得た。
<Comparative Example 7>
800 mg of the synthesized polymethacrylate of chemical formula (16), 100 mg of acetylene black and 100 mg of polytetrafluoroethylene resin binder were weighed and mixed in an agate mortar. Thereafter, the same method as in Comparative Example 1 was performed to obtain a coin-type electricity storage device.
本実施例１において作製した蓄電デバイスの開放電位は２．９Ｖであった。次に、得られた蓄電デバイスに対し、０．１１３ｍＡの定電流で充電を行い、電圧が４．０Ｖまで上昇した時点で充電を終了した。充電後の蓄電デバイスを分解し、正極を分析するとラジカル濃度の減少が観測され、対応する２，２，６，６−テトラメチルピペリジノキシルカチオンの生成が確認された。このカチオンは電解質アニオンＰＦ6 -によって安定化されている。 The open circuit potential of the electricity storage device manufactured in Example 1 was 2.9V. Next, the obtained electricity storage device was charged with a constant current of 0.113 mA, and the charging was terminated when the voltage rose to 4.0V. When the power storage device after charging was disassembled and the positive electrode was analyzed, a decrease in radical concentration was observed, confirming the formation of the corresponding 2,2,6,6-tetramethylpiperidinoxyl cation. This cation is stabilized by the electrolyte anion PF 6 − .
同様にして蓄電デバイスを作製し、０．１１３ｍＡの定電流で充電を行い、電圧が４．０Ｖまで上昇した直後に放電を行った。放電は、充電時と同じ０．１１３ｍＡの定電流で行い、電圧が３．０Ｖに達した時点で放電を終了した。放電時において、３．５Ｖ付近に電圧平坦部が認められた。この電圧平坦部は、正極で起こっているニトロキシルカチオンからニトロキシルラジカルに変化する還元反応と、負極で起こっているリチウムメタルのイオン化反応との間の電位差に相当することが分かった。すなわちこれは、本実施例１による蓄電デバイスが、化学電池として動作していることを示す結果である。本実施例１における平均放電電圧は、３．５２Ｖであった。 Similarly, an electricity storage device was fabricated, charged at a constant current of 0.113 mA, and discharged immediately after the voltage rose to 4.0V. Discharging was performed at the same constant current of 0.113 mA as that at the time of charging, and the discharging was terminated when the voltage reached 3.0V. At the time of discharge, a flat voltage portion was observed near 3.5V. It was found that this voltage flat portion corresponds to a potential difference between a reduction reaction that changes from a nitroxyl cation occurring at the positive electrode to a nitroxyl radical and an ionization reaction of lithium metal that occurs at the negative electrode. That is, this is a result indicating that the electricity storage device according to Example 1 is operating as a chemical battery. The average discharge voltage in Example 1 was 3.52V.
同様にして実施例２〜１０、比較例１〜７において作製した蓄電デバイスの充放電挙動を測定した。表１に実施例１〜実施例１０および比較例１〜７における、０．１１３ｍＡの定電流放電時の平均放電電圧についてまとめる。正極活物質および負極活物質が同じ種類の場合、平均放電電圧が高いほど蓄電デバイスの内部抵抗が小さく、平均放電電圧が低いほど内部抵抗が大きいことになる。実施例１と比較例１とを比較すると、正極と正極用金属集電体との間にカーボンペーパーを挟むことで、蓄電デバイスの平均放電電圧が高くなる、すなわち内部抵抗が小さくなることが分かる。実施例２〜４と比較例２〜４とを比較すると、化学式１７〜１９のいずれの正極活物質においても、正極と正極用金属集電体との間にカーボンペーパーを挟むことで、蓄電デバイスの平均放電電圧が高くなる、すなわち内部抵抗が小さくなることが分かる。実施例５と比較例５とを比較すると、負極活物質としてグラファイトを用いた場合でも、正極と正極用金属集電体との間にカーボンペーパーを挟むことで、蓄電デバイスの平均放電電圧が高くなる、すなわち内部抵抗が小さくなることが分かる。実施例６、７と比較例６、７とを比較すると、正極中に占める正極活物質の割合が１０％および８０％の場合でも、正極と正極用金属集電体との間にカーボンペーパーを挟むことで、蓄電デバイスの平均放電電圧が高くなる、すなわち内部抵抗が小さくなることが分かる。また、正極中に占める正極活物質の割合が８０％の場合には、その効果が一段と大きくなることが分かる。実施例８、９と比較例１とを比較すると、カーボンペーパーの厚みが０．０５ｍｍおよび０．２５ｍｍの場合でも、蓄電デバイスの平均放電電圧が高くなる、すなわち内部抵抗が小さくなることが分かる。実施例１０と比較例１とを比較すると、カーボンペーパーの種類が布状構造の場合でも、蓄電デバイスの平均放電電圧が高くなる、すなわち内部抵抗が小さくなることが分かる。 Similarly, the charge / discharge behavior of the electricity storage devices prepared in Examples 2 to 10 and Comparative Examples 1 to 7 was measured. Table 1 summarizes the average discharge voltage during constant current discharge of 0.113 mA in Examples 1 to 10 and Comparative Examples 1 to 7. When the positive electrode active material and the negative electrode active material are the same type, the higher the average discharge voltage, the smaller the internal resistance of the electricity storage device, and the lower the average discharge voltage, the larger the internal resistance. Comparing Example 1 and Comparative Example 1, it can be seen that sandwiching the carbon paper between the positive electrode and the positive electrode metal current collector increases the average discharge voltage of the electricity storage device, that is, reduces the internal resistance. . When Examples 2 to 4 and Comparative Examples 2 to 4 are compared, in any positive electrode active material represented by Chemical Formulas 17 to 19, an electric storage device is obtained by sandwiching carbon paper between the positive electrode and the positive electrode metal current collector. It can be seen that the average discharge voltage increases, that is, the internal resistance decreases. When Example 5 and Comparative Example 5 are compared, even when graphite is used as the negative electrode active material, the average discharge voltage of the electricity storage device is increased by sandwiching the carbon paper between the positive electrode and the positive electrode metal current collector. That is, it can be seen that the internal resistance is reduced. Comparing Examples 6 and 7 with Comparative Examples 6 and 7, even when the ratio of the positive electrode active material in the positive electrode was 10% and 80%, the carbon paper was placed between the positive electrode and the positive electrode metal current collector. It turns out that the average discharge voltage of an electrical storage device becomes high, ie, internal resistance becomes small by pinching. Further, it can be seen that when the proportion of the positive electrode active material in the positive electrode is 80%, the effect is further increased. When Examples 8 and 9 are compared with Comparative Example 1, it can be seen that even when the thickness of the carbon paper is 0.05 mm and 0.25 mm, the average discharge voltage of the electricity storage device increases, that is, the internal resistance decreases. When Example 10 and Comparative Example 1 are compared, it can be seen that even when the type of carbon paper is a cloth-like structure, the average discharge voltage of the electricity storage device increases, that is, the internal resistance decreases.
本発明による蓄電デバイスは、内部抵抗が小さいので、高い出力を必要とする蓄電デバイスとして利用することができる。本発明の活用例としては、従来、電気二重層キャパシタや鉛蓄電池、ニッケル水素電池、リチウムイオン二次電池等が用いられていた、パソコンやサーバーのバックアップ電源、電気自動車用の補助電源、携帯機器用電源等が挙げられる。 The electricity storage device according to the present invention has a low internal resistance, and thus can be used as an electricity storage device that requires high output. As examples of use of the present invention, conventionally, an electric double layer capacitor, a lead storage battery, a nickel metal hydride battery, a lithium ion secondary battery or the like has been used, a backup power source for a personal computer or server, an auxiliary power source for an electric vehicle, a portable device Power supply and the like.
１ 負極用金属集電体
２ 絶縁パッキン
３ 負極
４ セパレータ
５ 正極
６ カーボンペーパー
７ 正極用金属集電体
DESCRIPTION OF SYMBOLS 1 Metal collector for negative electrodes 2 Insulation packing 3 Negative electrode 4 Separator 5 Positive electrode 6 Carbon paper 7 Metal collector for positive electrodes
Claims (3)
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| JP2004038721A JP4530133B2 (en) | 2004-02-16 | 2004-02-16 | Power storage device |
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| JP4506955B2 (en) * | 2004-07-07 | 2010-07-21 | 三菱瓦斯化学株式会社 | Method for producing copolymer composition having stable radical |
| JP4943106B2 (en) * | 2006-09-26 | 2012-05-30 | 住友精化株式会社 | Method for producing (meth) acrylic acid-based crosslinked copolymer |
| JP2008135371A (en) * | 2006-10-27 | 2008-06-12 | Denso Corp | Secondary battery active substance and secondary battery |
| FR2913979A1 (en) * | 2007-03-20 | 2008-09-26 | Arkema France | PROCESS FOR THE PREPARATION OF POLYMERS WITH NITROXIDE FUNCTIONS |
| JP5573749B2 (en) * | 2011-03-25 | 2014-08-20 | 株式会社デンソー | Non-aqueous electrolyte battery |
| JP6720350B2 (en) | 2016-06-02 | 2020-07-08 | エボニック オペレーションズ ゲーエムベーハー | Method for manufacturing electrode material |
| JP6650054B2 (en) | 2016-09-06 | 2020-02-19 | エボニック オペレーションズ ゲーエムベーハー | Improved oxidation of secondary amino groups |
| CN114207917B (en) | 2019-08-20 | 2024-06-14 | 麦克赛尔株式会社 | All-solid battery |
| CN111235595B (en) * | 2020-01-20 | 2021-05-25 | 常州大学 | TEMPO-based polypyrrole for mixed liquid flow battery cathode and preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61245468A (en) * | 1985-04-23 | 1986-10-31 | Toyota Central Res & Dev Lab Inc | Nonaqueous electrolyte storage battery |
| JP2000037852A (en) * | 1998-07-20 | 2000-02-08 | Heidelberger Druckmas Ag | Printer having blanket body with filling bar and blanket |
| JP2002304996A (en) * | 2001-04-03 | 2002-10-18 | Nec Corp | Electric storage device |
| WO2005078830A1 (en) * | 2004-02-16 | 2005-08-25 | Nec Corporation | Electric storage device |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61245468A (en) * | 1985-04-23 | 1986-10-31 | Toyota Central Res & Dev Lab Inc | Nonaqueous electrolyte storage battery |
| JP2000037852A (en) * | 1998-07-20 | 2000-02-08 | Heidelberger Druckmas Ag | Printer having blanket body with filling bar and blanket |
| JP2002304996A (en) * | 2001-04-03 | 2002-10-18 | Nec Corp | Electric storage device |
| WO2005078830A1 (en) * | 2004-02-16 | 2005-08-25 | Nec Corporation | Electric storage device |
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| JP2005228705A (en) | 2005-08-25 |
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